Urethane derivatives of polymethyl biphenyl

ABSTRACT

Novel urethane derivatives of polymethyl biphenyl useful as fungicides and also having insecticidal, miticidal and nematocidal activities are disclosed. These products are prepared by reacting the appropriate alkyl or aryl chloroformate with the appropriate amino polymethylbiphenyl at temperatures of 0 to 35*C. to produce the corresponding urethane derivatives of polymethyl biphenyl.

United States Patent [1 1 Puskas et al.

May 6, 1975 URETHANE DERIVATIVES OF POLYMETHYL BIPHENYL Inventors: Imre Puskas, Glen Ellyn; Ellis K.

Fields, River Forest, both of I11.

Assignee: Standard Oil Company, Chicago, Ill. Filed: Jan. 24, 1972 Appl. No.: 220,368

US. Cl 260/471 C; 260/455 A; 424/300 Int. Cl C07c 125/06 Field of Search 260/47] C References Cited UNITED STATES PATENTS 7/1971 Teach et al. 260/47l C Primary Examiner-Lorraine A. Weinberger Assistant Examiner-L. A. Thaxton Attorney, Agent, or FirmGunar J. Blumberg; Arthur G. Gilkes; William T. McClain [5 7 ABSTRACT Novel urethane derivatives of polymethyl biphenyl useful as fungicides and also having insecticidal, miticidal and nematocidal activities are disclosed. These products are prepared by reacting the appropriate alkyl or aryl chloroformate with the appropriate amino polymethylbiphenyl at temperatures of 0 to 35C. to produce the corresponding urethane derivatives of polymethyl biphenyl.

1! Claims, No Drawings URETHANE DERIVATIVES F POLYMETHYL BIPHENYL This invention relates to novel urethane derivatives of polymethyl biphenyl. More particularly, this invention relates to urethane derivatives of polymethyl biphenyls having the following formula:

wherein the NH-CO-XR group occupies the two or three position on the phenyl ring, and wherein X is oxygen or sulfur, R is an alkyl, aryl or substituted aryl group and R, and R, are methyl groups and n and m are integers having values from 2 through 4 inclusive.

These novel compositions have extraordinary fungicidal activity. The compositions of this invention are effective fungicides as well as insecticides, miticides, nematocides and herbicides. They are thus highly valuable and useful in providing actions in single spray or dust which are ordinarily obtained only by combining a variety of different fungicidal and insecticidal agents or by the application of a series of insecticidal and fungicidal compositions. These novel fungicidal compositions are prepared by reacting the amino biphenyl with the corresponding alkyl or aryl chloroformate in pyridine under anhydrous conditions at a temperature of 0 to 35C. The amino biphenyl has the following structure:

4 dimethylphenyl )=4,5=dimethylear= 2 Phenyl 2-(3,4'-dimethylphenyl)-4,5-dimethylcarbanilate Phenyl 2-( 3 ',4'-dimethylphenyl )-4,5-dimethylthiocarbanilate 5 Ethyl 2-(2,4-dimethylphenyl )-4,5-dimethylcarbanilate Methyl 2,4,6-trimethyl-3-( 3',4'-dimethylphenyl) carbanilate Ethyl 2,4,6-trimethyl-3-(3',4'-dimethylphenyl) carbanilate lsopropyl 2,4.6-trimethyi-3-(3,4'-dimethylphenyl)- carbanilate Phenyl 2,4,6-trimethyl-3-(3,4-dimethylphenyl) carbanilate Phenyl 2,4,6-trimethyl-3-(3',4'-dimethylphenyl)-thio( l )-carbanilate lsopropyl 2,3,4,5-tetramethyl-6(3',4'-dimethylphenyl)carbanilate Methyl 2,4,6-trimethyl3-(2,4',6'-trimethylphenyl) carbanilate lsopropyl 2,4,6-trimethyl-3-(2,4',6'-trimethylphenyl)carbanilate In a representative example, 3-amino-2,3',4,4',6- pentamethyl biphenyl (1.9 g.) was dissolved in dry pyridine (15 ml.). The solution was cooled to 0C. and stirred while ethyl chloroformate (0.92 ml.) was introduced dropwise. After an hour stirring the solvent was removed in vacuo. The residue was taken up in ether and extracted with water, dilute hydrochloric acid and water, successively. From the ether layer, after removal of the solvent, a semi-solid material was obtained. This, from a small amount of hexane, gave white prisms of the urethane which melted at 86 to 91C. This composition induced 100, 100 and 93 percent control of Powdery Mildew on squash, respectively, at 1,000, 500 and 250 parts per million, thus showing its utility as a fungicide.

The invention is further illustrated in the following examples.

EXAMPLE I At 0C, methyl chloroformate (l.l6 ml.) was added dropwise to a stirred solution of 2-amino-3',4,4',5-tetramethylbiphenyl (3.37 g.) in 4-picoline (1.5 ml.) and toluene (20 ml.). After 30 minutes reaction time, the solvents were removed in vacuo. The residue was partitioned between ether and water. The organic layer was washed with water and dried over sodium sulfate. Removal of the ether left a liquid. This was crystallized from hexane (9 ml.) at 0C. to give 66% yield of white crystals of the methyl 2-(3',4'-dimethylphenyl)-4,5- dimethylcarbanilate, in the first crop, m.p. 72-73C.

Its IR spectrum showed NJ! band at 3250 cm and C band at 1696 cm (in Nujol mull).

Methyl 2-(3',4'-dimethylphenyl)4.5-dimethylcarhanilate prepared as shown in Example 1 was tested for foliar fungicidal efficacy. The results are shown in the following table:

The experiment was analogous to Example 1, but in place of methyl chloroformate, ethyl chloroforrnatc (1.42 ml.) was used. The product, ethyl 2-(3',4'- dimethylphenyi)-4.S-dimethylcarhanilate, was a liquid. lts IR spectrum showed N-H hand at 3370 cm and C=O band at 1735 cm (heat liquid between NaCl plates).

EXAMPLE lll At 0C. ispropyl chloroformate (0.62 ml.) was added dropwise to a stirred solution of 2-amino-3',4,4',5-tetramethylbiphenyl (1.154 g.) in anhydrous pyridine (15 ml.). After 30 minutes reaction time, the solvents were removed in vacuo. Residue was extracted between ether and water. The organic layer was washed with water and dried over sodium sulfate. Removal of the ether left a syrup (1.38 g.), ispropyl 2-(3,4'- dimethylphenyl)-4.S-dimethylcarbanilate. lts 1R spec trum showed N'H band at 3400 cm and (:0 band at 1745 cm (neat liquid between NaCl plates).

EXAMPLE IV At 0C phenyl chloroformate (1.40 ml.) was added dropwise to a stirred solution of 2-amino-3',4,4',5-tetramethylbiphenyl (2.48 g.) in anhydrous 4picoline (1.1 m1.) and toluene (20 ml.). The workup procedure of Example l have 3.31 g. of phenyl 2-(3',4'- dimethylphenyl1-4,idimethylcarbanilate as white crystals. mp. 1171l9C. lts IR spectrum showed the expected N-H and C=O bands at 3330 and i745 cm, respectively (in Nujol mull).

EXAMPLE V At 0C. phenyl thiochloroformate (1.31 ml.) was added dropwise to a stirred solution of 2-amino- 314.4,5-tctramethylbiphenyl (2.25 g.) in anhydrous 4-picoline ml.) and to1ucne(20m1.). The workup procedure of Example 1 gave a syrup that was dried in 0.3 mm. vacuo at room temperature; the syrup did not crystallize. The lR spectrum of the phenyl 2-(3,4'- dimethylphenyl)4,S-dimethylthiocarbanilate product showed the N-H and C=O bands at 3340 and 1690 cm, respectively (neat liquid between NaCl plates).

EXAMPLE Vl At 0C. ethyl chloroformate (0.92 ml.) was added dropwise to a stirred solution of 2-amino-2,4,4',5-tetramethylhiphenyl (1.85 g.) in anhydrous pyridine (15 ml. The workup procedure of Example I gave 226 g. white product of ethyl 2-(2,4'-dimethylphenyl)-4,5- dimethylcarbanilate, m.p. l0l104C. lts IR spectrum showed the N-H and C=O bands at 3400 and 1735 cm, respectively (in Nujol mull).

EXAMPLE Vll At 0C. methylchloroformate (0.81 ml.) was added dropwise to a stirred solution of 3-amino-2,3',4,4,6- pentamethylbiphenyl (2.39 g.) in anhydrous pyridine 15 ml.). After 30 minutes reaction time, the solvents were removed in vacuo. The residue crystallized on being triturated with water. The crystals were washed with a little hexane and dried in vacuo to give methyl 2.4,6-trimethyl-343',4'-dimcthylphenyl) carbanilate, m.p. 126128C. its IR spectrum showed the N-H and C=O bands at 3250 and 1695 cm", respectively (in Nujol mull).

EXAMPLE Vlll At 0C. ethyl chloroformate (0.92 ml.) was added dropwise to a stirred solution of 3-amino-2,3',4,4,6- pentamethylbiphenyl (1.9 g.) in anhydrous pyridine (15.0 ml.). After 30 minutes reaction time, the solvents were removed in vacuo. The residue was partitioned between ether and water. The organic layer was washed with dilute aqueous hydrochloric acid. then water, and dried over sodium sulfate. Removal of the ether left a semi-solid which was crystallized from a small quantity of hexane. The product, ethyl 2,4,6- trimethyl-3-(3',4'-dimethylphenyl) carbanilate. melted at 869lC. its IR spectrum showed the N-H and (:0 bands at 3280 and 1685 cm, respectively (in Nujol mull).

EXAMPLE IX At 0C. isopropyl chloroformate (1.25 ml.) was added dropwise to a stirred solution of 3-amin0- 2,3',4,4',6-pentamethylbiphenyl (2.39 g.) in anhydrous pyridine (15 ml.). After 30 minutes reaction time. the solvents were removed in vacuo. The residue cystallized on being triturated with water. The crystals were dried in vacuo and recrystallized from hexane. The white product, isopropy] 2,4,6-trimethyl-3-(3',4- dimethylphenyl) carbanilate, melted around 90C.; the melting range depended on the rate of heating. lts IR spectrum showed the N-H and (=0 bands at 3230 and 1680 cm". respectively (in Nujol mull).

EXAMPLE X At 0C. phenyl chloroformate (1.4 ml.) was added dropwise to a stirred solution of 3amino-3,3',4,4',6- pentamethylhiphenyl (2.63 g.) in anhydrous 4-picoline (1.1 ml.) and toluene (20 ml. The workup procedure of Example I gave 3.55 g. of white crystals,pheny12,4,- 6-trimethyl-3-(3',4'-dimethylphenyl) carbanilate. m.p. 123-125C. lts IR spectrum showed the N-H and C=O bands at 3220 and 1720 cm. respectively (in Nujol mull).

EXAMPLE X1 crystallized on being triturated with water. The crude product. methyl 2,4,6-trimethyl-3-(2,4',h trimethylphenyl) carbanilate, l.94 g. melted at l-l 36C. Its IR spectrum showed the N-H and (:0 bands at 3280 and 1710 cm, respectively (in Nujol mull).

At 0C. phenyl thiochloroformate (1.3l ml.) was added dropwise to a stirred solution of 3-amino- 2,3,4,4',6-pentamethylbiphenyl (2.39 g.) in anhydrous 4-picoline (1.0 ml.) and toluene (20 ml.). After minutes reaction time, the solvents were removed in vacuo. The residue was extracted between an ether- EXAMPLE XIV benzene mixture and water. The organic layer was washed and dried over sodium sulfate. The solution was g concentrated; the product phenyl 24.6 trimethy| 3 wise to a stirred solution of aminobimesityl (1., g.) m (3' 4 dimethylphenyl) thiocarbanilate crystallized anhydrous pyndme 15 The workup f i of 3 g m p 1500451: Its IR showed um Example Vlll gave a sohd foam, m.p. 40-55C '1 he [R spectrum of the isopropyl 2.4,6-trimethyl-3-(2'.4'.h'- C20 bands at 3225 and 1670 cm respectively (m trimethylphenyl) carbanilate showed the expected N-H isopropyl chloroformate (1.3 ml.) was added drop- Nujol mu). 5 and C=O bands at 3200 and 1700 cm". respectively EXAMPLE Xll (in Nujol mull).

At 0C. isopropyl chloroformate (0.70 ml.) was We claim: added dropwise to a stirred solution of 2-amino- LA urethane derivative ofpolymethylbiphcnyl hav- 3,3',4,4,5,fi-hexamethylbiphenyl (1.35 g.) in anhy- 20 ing the following formula:

( (Fight -co-m' drous pyridine (15 ml.). After 30 minutes reaction wherein the NHCOXR occupies the two or three time, the solvents were removed in vacuo. The syrupy position on the phenyl ring. and wherein X is oxygen, residue was digested with water. dried in vacuo, and R is a lower alkyl, or phenyl radical and R and R are crystallized from hexane (about 8 ml.). The white methyl groups and n and m are integers having values product, isopropyl 2.3,4,5-tetramethyl-6-(3',4' from 2 through 4 inclusive.

dimethylphenyl) carbanilate (1.52 g.), melted at 2. A urethane derivative of polymethylhiphenyl hav- 1 l3-l 15C. lts IR spectrum showed the C=O band at ing the following formula:

1710 cm; surprisingly there were two bands in the N-H stretching region at 3090 and 3180 cm (in Nujol CH 3 mull).

EXAMPLE XIII 33C I \\I j/ CH Fuming 90% nitric acid (3.6 ml.) was added dropwise to a stirred solution of bimesityl (l2.0 g.) in a 1:1 mixture of acetic acid-acetic anhydride (40 ml.). The mix- NH CO-OCH3 ture was heated to 50C" pOured on and 3. A urethane derivative of polvmethylhiphenvl havtracted with ether. The organic layer was washed with ing the fonowing formua: aqueous sodium hydroxide free of acid, then with water. Removal of the ether left crystals of crude ni- CH CH trobimesityl, m.p. 9496C. This was used in the next 3 N V step without further purification. CH

A mixture of nitrobimesityl (4.0 g.), ethanol (70 3 3 ml.), 65% hydrazine (10 m1.) and a spatula tip of wet i Raney nickel was refluxed for three hours. Removal of the solvent from the filtered solution gave m! CH aminobimesityl as white crystals, (2.5 g.), m.p. 3

]48.5-l49.5C. The structure was confirmed by IR C0-0-CH CH and mass spectrometry.

Methyl chloroformate (1.0 ml.) was added dropwise 4. The urethane of claim 1 wherein X is Oxygen and to a stirred solution of aminobimesityl (1.7 g.) in why R is an ethyl group, n and m are integers each having drous pyridine (15 ml.). After the exothermic reaction a value of 2 and wherein the methyl groups are atthe solvents were removed in vacuo. The residue slowly tached on the 4.5 and 4,5' positions on the hiphcnyl rings, and the NHCOXR' group occupies the 2 position on the biphenyl ring.

5. The urethane of claim 1 wherein X is oxygen and R is an isopropyl group. n and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4',5' positions on the biphenyl rings, and the NH-COXR' group occupies the 2 position on the biphenyl ring 6. The urethane of claim I wherein X is oxygen and R is a phenyl group. n and m are integers each having a value of 2, and wherein the methyl groups are attached on the 4,5 and 4',5' positions on the biphenyl ring, and the NH-COXR' group occupies the 2 position on the biphenyl ring.

7. The urethane of claim 1 wherein X is oxygen and R is an ethyl group, n and m are integers each having a value of 2, and wherein the methyl groups are attached on the 4,5 and 2',4' positions on the biphenyl rings. and the NHCOXR' group occupies the 2 position on the biphenyl ring.

8. The urethane of claim 1 wherein X is oxygen and R is a methyl group. n and m are integers having values 3 and 2, respectively, and wherein the methyl groups are attached on the 24,6 and 4',5' positions on the biphenyl rings, and the NHCOXR group occupies the 3 position on the biphenyl ring.

9. The urethane of claim 1 wherein X is oxygen and R is an isopropyl group, n and m are integers having values 3 and 2, respectively, and wherein the methyl groups are attached on the 2,4,6 and 4,5' positions on the biphenyl rings, and the NHCOXR' group occupies the 3 position on the biphenyl ring.

10. The urethane of claim 1 wherein X is oxygen and R is a phenyl group, n is an integer having a value of 3 and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4',5' positions on the biphenyl rings, and the NH-CO-XR' group occupies the 3 position on the biphenyl ring.

11. The urethane of claim 1 wherein X is oxygen and R is an isopropyl group, n is an integer having a value of 4 and m is an integer having a value of 2, and wherein the methyl groups are attached on the 3,4,5,6 and 4',5' positions on the biphenyl ring, and the NH COXR group occupies the 2 position on the biphenyl ring. 

1. A URETHANE DERIVATIVE OF POLYMETHYLBIPHENYL HAVING THE FOLLOWING FORMULA:
 2. A urethane derivative of polymethylbiphenyl having the following formula:
 3. A urethane derivative of polymethylbiphenyl having the following formula:
 4. The urethane of claim 1 wherein X is oxygen and R'' is an ethyl group, n and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4'',5'' positions on the biphenyl rings, and the NH-CO-XR'' group occupies the 2 position on the biphenyl ring.
 5. The urethane of claim 1 wherein X is oxygen and R'' is an isopropyl group, n and m are integers each having a value of 2 and wherein the methyl groups are attached on the 4,5 and 4'',5'' positions on the biphenyl rings, and the NH-CO-XR'' group occupies the 2 position on the biphenyl ring.
 6. The urethane of claim 1 wherein X is oxygen and R'' is a phenyl group, n and m are integers each having a value of 2, and wherein the methyl groups are attached on the 4,5 and 4'',5'' positions on the biphenyl ring, and the NH-CO-XR'' group occupies the 2 position on the biphenyl ring.
 7. The urethane of claim 1 wherein X is oxygen and R'' is an ethyl group, n and m are integers each having a value of 2, and wherein the methyl groups are attached on the 4,5 and 2'',4'' positions on the biphenyl rings, and the NH-CO-XR'' group occupies the 2 position on the biphenyl ring.
 8. The urethane of claim 1 wherein X is oxygen and R'' is a methyl group, n and m are integers having values 3 and 2, respectively, and wherein the methyl groups are attached on the 2,4,6 and 4'',5'' positions on the biphenyl rings, and the NH-CO-XR'' group occupies the 3 position on the biphenyl ring.
 9. The urethane of claim 1 wherein X is oxygen and R'' is an isopropyl group, n and m are integers having values 3 and 2, respectively, and wherein the methyl groups are attached on the 2,4,6 and 4'',5'' positions on the biphenyl rings, and the NH-CO-XR'' group occupies the 3 position on the biphenyl ring.
 10. The urethane of claim 1 wherein X is oxygen and R'' is a phenyl group, n is an integer having a value of 3 and m is an integer having a value of 2, and wherein the methyl groups are attached on the 2,4,6 and 4'',5'' positions on the biphenyl rings, and the NH-CO-XR'' group occupies the 3 position on the biphenyl ring.
 11. The urethane of claim 1 wherein X is oxygen and R'' is an isopropyl group, n is an integer having a value of 4 and m is an integer having a value of 2, and wherein the methyl groups are attached on the 3,4,5,6 and 4'',5'' positions on the biphenyl ring, and the NH-CO-XR'' group occupies the 2 position on the biphenyl ring. 